US3871972A - Electrorecording sheet - Google Patents

Electrorecording sheet Download PDF

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Publication number
US3871972A
US3871972A US320821A US32082173A US3871972A US 3871972 A US3871972 A US 3871972A US 320821 A US320821 A US 320821A US 32082173 A US32082173 A US 32082173A US 3871972 A US3871972 A US 3871972A
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United States
Prior art keywords
color
color forming
electroconductive layer
electro
recording sheet
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Expired - Lifetime
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US320821A
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English (en)
Inventor
Yoichi Sekine
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current

Definitions

  • the present invention relates to an electrorecording sheet which directly converts an electric signal into a visible image and in which a layer of cuprous iodide as an electroconductive layer is provided in contact with a color forming layer capable of providing a visible record when current is applied thereto.
  • such recording sheets are desired which can be used in the light, can attain a recording of high gradient at high speed, can be stably stored without discoloration or fading, are inexpensive and require no such operations as change of head, supply of ink, etc.
  • the present invention provides an electrorecording sheet which substantially meets the above mentioned requirements.
  • This electrorecording sheet comprises an electroconductive layer of cuprous iodide having applied thereon a color forming layer containing a substance capable of causing color formation or visual color change due to electrochemical reaction or heat energy which results when current corresponding to the electric signal is passed therethrough.
  • This recording sheets forms a colored visible image near a recording needle electrode on the color forming layer due to electrochemical oxidation, reduction or formation of heat energy by applying current between the recording needle electrode and an oppositeelectrode which are allowed to contact with the recording sheet.
  • the spark destructive recording sheet which resembles the present recording sheet can also attain a high speed recording.
  • the spark destructive recording sheet uses carbon or metal film formed by vacuum evaporation as an electroconductive layer, it cannot be made into a copying base paper which utilizes transmitting light.
  • the color forming mechanism of the spark destructive recording sheet is that a masking layer is removed by spark to make a colored layer therebelow visible. Therefore, a large amount of pigment is required for masking the electroconductive layer of carbon or a metal and the colored layer and this necessarily causes generation of bad smell and recording sludge due to spark at recording.
  • FIG. 1 is a drawing which shows a fundamental construction of the recording sheet of the present invention
  • FIG. 2 is a drawing which illustrates a recording method using said recording sheet.
  • 1 is a support such as paper, fabric, glass, plastic film, etc. and 2 is an electroconductive layer comprising cuprous iodide.
  • This electroconductive layer can be produced by vacuum evaporation of cuprous iodide onto the surface of support 1 or by dispersing fine particles of cuprous iodide in an appropriate binder solution and coating the solution on the surface of support 1.
  • This binder must be one which does not melt during storage.
  • Preferable binders are those which do not melt at a temperature less than C.
  • the surface resistivity of the electroconductive layer 2 is the lower, the better and is preferably less than 10 0 at 20C and at a relative humidity of 65 percent.
  • color forming layer 3 is a color forming layer containing a component which is capable of color forming with mainly heat energy generated when current corresponding to electric signal to be recorded is applied. This color forming component will be detailedly explained hereinafter.
  • color forming layer 3 is provided on the surface of electroconductive layer 2, but the electroconductive layer can be provided on the surface of the color forming layer.
  • HEAT RECORDING MATERIALS These cause color formation by heat energy generated when electric current is applied.
  • One of them utilizes coupling due to formation of reaction product of an electron donor and an electron acceptor.
  • ferric stearate as an electron donor and pyrogallol as an electron acceptor are separately dispersed in a binder and the binder is softened with heat to melt ferric stearate, thereby to attain recording. In this case, dark brown colored record is obtained.
  • These heat recording materials include combination of leuco form of triphenylmethane dyes such as crystal violet lactone 0r leuco form of fluoran dyes and an organic acid or a phenolic acidic material or combination of an organic compound having metal ion and an organic spot test reagent. These dyes and organic acid and organic metal compound and organic spot test reagent are separately dispersed in a binder.
  • Lactum (Rhodnmine B lactam) of 9-p-nitroanilino-3,6-bis(diethylamino)-9- xanthenyl-o-benzoic acid;
  • the above enumerated dye bases are effective and hardly dissolve in water and can be ground into less than 10 u.
  • Color forming agent As the color forming agents which react with the color forming dyes mentioned in the above (a) to form dyes, phenolic compounds or organic acids are preferred. These are preferably solid at normal temperature and liquefied or gasified at higher than 70C.
  • PHENOLIC COMPOUNDS 3,5-xylenol; thymol; 4-tertiary-butyl phenol; 4-hydroxyphenoxide; methyl-4-hydroxybenzoate; 4-hydroxyacetophenone; a-naphthol; B-naphthol; catechol; hydroquinone; resorcin; 4-tertiaryoctyl catechol; 4,4-secondarybutylidenediphenol: 2,2'-dihydroxydiphenyl; 2,2'-methylene bis (4-methyl-6-tertiarybutyl phenol); 2,2-bis(4- oxyphenyl)-propane; 4,4-isopropylidene bis(2- tertiarybutyl phenol); 4,4'-secondarybutylidene diphenol; pyrogallol: 4,4'-isopropylidenediphenol.
  • Organic spot test reagents and organic metal salts are those which react with metal ion to result in coloration or change in color and a great number of substances are known as said reagents. However, since the fact that at least one of the two are molten by heat energy generated upon application of electric current and the two react with each other to form color is utilized, it is preferred that one of them which has lower melting point is solid at lower than C and has a melting point of lower than C. For this reason,'organic metal salt (metallic soap) is the most suitable. Combinations of the organic spot test reagents and the metal are as follows:
  • Organic spot test reagents Metal Diphenylthiocarbazide: Cu, Fe, Mg, Hg
  • Rhodamine Cu, Hg Diphenylthiocarbasone: Cu, Ba, Co, Fe, Pb, Hg, Zn
  • Diphenylcarbasone Co, Cu, Pb, Mg, Mn, Hg, Ni, Zn
  • Dithioxamide Co, Cu, Pb, Ni
  • Organic metal salts Metallic soa ps contaiiiing metal ion as mentioned be fore are effective. Typical combinations of the organic spot test reagents and the organic metal salts and formed color are shown below.
  • Organic spot test reagents Organic metal salts (color) Dimethylglyoxime: Nickel stearate (Pink color) Benzoinoxime: Copper myristate (Yellowish green) Dithioxamide: Nickel stearate (Purple) 8-Hydroxyquinoline: Ferric oleate (Black) Gallic acid: Ferric stearate (Black) Alizarin: Copper oleate (Purple red) Quinalizarin: Copper oleate (Purple red) Diphenylcarbasone: Ferric stearate (Red) Diphenylcarbasone: Cadmium stearate (Red) Diphenylcarbazone: Copper myristate (Purple) Diphenylcarbazone: Zinc palmitate (Deep red) Diphenylthiocarbazide: Mercuric stearate (Purple) Diphenylthiocarbazidc: Lead myristate (Deep red) d.
  • oxidation-reduction indicator form color at the portion at a recording needle upon application of electric current and it has been confirmed that they are effective as color forming materials of electrorecording sheet.
  • the oxidation-reduction indicators used herein are those which are oxidized by heat generated upon application of electric currentto form color or change color and are all in leuco form.
  • the oxidationreduction indicators used in the present invention and color thereof are shown below.
  • Leucoethyl Nile Blue (Blue) Leucomethyl Capryl Blue (Blue) Leucotoluyl Blue (Purple) Leuco diphenyl amine (Purple) Leuco-N-methyldiphenylamine-p-sulfonic (Reddish purple) Leuco phenyl anthranyl acid (Reddish purple) Triphenyltetrazonium chloride (Red) Methylviologen(Purple) Leuco Safranine T (Red) Leuco indigo sulfonic acid (Blue) Leuco Phenosafranine (Red) Leucomethylene Blue (Blue) Leucodiphenylbenzidine (Purple) Leuco Erioglaucine A (Yellowish green Red) Leuco-p-nitrodiphenylamine (Purple) Leucodiphenyl-o,o-diphenylcarboxylic acid (Bluish purple) e.
  • Metal chlorides and oxides herein mentioned form visible marks by synergistic effect of heat generated upon application of electric current and electric action.
  • silver chloride in fine particle state is dispersed in a binder and therefrom a white color forming layer is formed on an electroconductive layer of cuprous iodide.
  • AgCl is reduced to Ag by application of electric current to result in brownish black colored trails of recording needle.
  • the metal chlorides and oxides used as color forming component and formed color are shown below.
  • BlNDERS Binders are used to disperse in fine particle state the color forming dyes and color forming agents, the organic spot test reagents and organic metal salts, etc. of the color forming layer or cuprous iodide of electro conductive layer and to impart them binding ability.
  • WATER SOLUBLE BlNDERS Hydroxyethylcellulose carboxymethylcellulose, methoxycellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, gelatin, starch.
  • R R and R are alkyl, allyl, aryl, acyl or alkylamino group and X is a halogen.
  • WATER INSOLUBLE BINDERS EXAMPLE 3 As binders, those which are soluble in organic solvent may also be used. When, for example, color forming dyes and color forming agents are used as color formg of cuprous iodide was mixed with 100 cc of aqueous solution containing 4 percent by weight of polyvinyl alcohol (PVA 205 manufactured by Kurare K.K.) and they were ground and mixed in a ball mill of content volume of 500 ml for 24 hours. Thus obtained dispersion was coated on an art paper with a wire bar which was adjusted to form a coating film of 15 u and the film was dried. Surface resistivity of the coated paper was (2 X 0.
  • PVA 205 polyvinyl alcohol
  • EXAMPLE 4 [00 gr of cuprous iodide was mixed with 100 cc of toluene solution containing 10 percent by weight of a 85 l5 copolymer of styrene and butadiene and they were ground and mixed in a ball mill of a content volume of 500 ml for 24 hours. Thus obtained dispersion was coated on an art paper with a wire bar adjusted for form a coating film of p. and this was dried. Surface resistivity of this coated paper was (4 7) X 10 9.
  • EXAMPLE 5 35 parts by weight of 3,6-dimethylfluorane (color forming dye) was mixed with 200 parts by weight of an aqueous solution containing 10 percent by weight of polyvinyl alcohol (PVA 205 manufactured by Kurare l(.K.) and they were ground and mixed in a ball mill of a content volume 500 ml for 48 hours.
  • a dispersion of color forming agent was prepared by mixing an aqueous solution containing 10 percent by weight of polyvinyl alcohol with 35 parts by weight of B-naphthol as a color forming agent.
  • the color forming dye and color forming agent in respective liquid were hardly dissolved and dispersed as fine particles of less .than 5 u.
  • One part by weight of the color forming dye dispersion and 10 parts by weight of color forming agent dispersion were mixed with a mixer.
  • the color forming dye and color forming agent were dispersed as fine particles in the mixed solution and since the particles were surrounded with polyvinyl alcohol, the particles did not directly contact with each other.
  • Thus obtained mixed solution as a solution for forming a color forming layer was coated on the deposited paper obtained in Example l with a wire bar adjusted to form a coating film of 8 10 p. and this was dried. Thereto was applied a direct current voltage of 70 V and recording was carried out as shown in FIG. 2 to obtain clear red record having a reflection density of 0.85.
  • As the recording needle a piano wire of 0.25 mm in diameter was used and as the face electrode, a carbon plate was used. The recording needle was moved at a speed of 200 mm/sec.
  • EXAMPLE 6 The mixed solution used for formation of color forming layer in Example 5 was coated on the deposited paper obtained in Example 3 in the same manner as in Example 5 and this was dried. To the resultant paper was applied a voltage of 400 V and recording was carried out under the same conditions as in Example 5 to obtain a red record having a reflection density of 0.5.
  • EXAMPLE 7 A mixed solution was prepared under the same conditions as in Example 5 except that ferric stearate and gallic acid were used as the color forming dye and color forming agent, respectively. The resultant solution was coated on the electroconductive paper obtained in Example 2 in a thickness of 8 10 u and was dried.
  • EXAMPLE 8 35 parts by weight of Leucomethylene Blue was blended with 200 parts by weight of an aqueous solution containing 30 percent by weight ofsodium polystyrene sulfate (Oligo Z manufactured by Tomoegawa Seishi K.K.) and they were ground and mixed in a ball mill of 500 ml for 48 hours.
  • the Leucomethylene Blue was dispersed in thus obtained liquid as flne particles of less than 5 ,u.
  • This mixed solution was coated on the electroconductive layer-coated paper obtained in Example 4 in a thickness of 8 10 p. and was dried. To the coated paper was applied a direct current voltage of 550 V and a recording needle as an anode was moved at a speed of 200 mm/sec. to obtain a blue recorded trace having a reflection density of 0.25.
  • EXAMPLE 9 200 parts by weight of lead chloride was blended with 200 parts by weight of a toluene solution containing 10 percent by weight of styrene/butadiene 1 15) copolymer and they were ground and mixed in a ball mill of content volume of 500 ml for 48 hours. This mixed solution was coated on the electroconductive paper obtained in Example 1 in a thickness of 10 p. and was dried. Thereto was applied a direct current voltage of 70 V and recording was carried out by moving a recording needle as a cathode to obtain a greyish black recorded trace having a reflection density of 0.4.
  • EXAMPLE 1'0 The mixed solution prepared in Example 5 was coated on a white paper in a thickness of 10 u.
  • This coated paper which was the so-called heat sensitive color forming paper was sticked to inner face of a bell jar as in Example 2 and copper was vacuum evaporated to the heat sensitive layer coated face of the paper.
  • This paper was placed in a desiccator and said copper was allowed to react with iodine while subjecting to suction with an aspirator to produce transparent and light yellow cuprous iodide. Thereto was applied a direct current voltage of 50 V and recording needle was moved at 200 mm/sec. to obtain a clear record having a reflection density of 0.9.
  • EXAMPLE 1 l 25 parts by weight of nickel stearate, 5 parts by weight of ethylcellulose and parts by weight of acetone were charged in a ball mill of content volume of 500 ml and they were ground and dispersed for 24 hours. Similarly, l0 parts by weight of dimethylglyoxine, 5 parts by weight of ethylcellulose and 100 parts by weight of acetone were mixed to prepare a dispersion. The two dispersions were mixed in a weight ratio of l l and were well agitated with a mixer. This mixed solution was coated on the electroconductive paper obtained in Example 4 in a thickness of 5 10 p. and was dried. Thus obtained recording paper formed a pink colored reocrd on light yellow ground upon application of electric current.
  • EXAMPLE 12 25 parts by weight of Crystal Violet Lactone, 5 parts by weight of styrene-butadiene copolymer resin and 100 parts by weight of toluene were ground in a ball mill for 24 hours to prepare a dispersion. Similarly, 25 parts by weight of Bisphenol A, 5 parts by weight of styrene-butadiene copolymer resin and 100 parts by weight of toluene were ground to prepare a dispersion. Then, the former dispersion and the latter dispersion were mixed in aweight ratio of 1 l and were well agitated. The resultant mixed solution was coated on the electroconductive paper obtained in Example 3 in a thickness of 5 [L and was dried. Thus obtained recording paper formed a clear blue record on white ground upon application of electric current.
  • An electro-recording sheet having an electroconductive layer of cuprous iodide which has a surface resistivity of less than 10 9 at a temperature of 20C and a relative humidity of 65 percent and a color forming layer provided in contact with said electroconductive layer and which forms a mark due to selective color formation or color change in the parts of said color formation layer to which electric current is applied through said electroconductive layer.
  • electroconductive layer comprises homogeneous component of only cuprous iodide wherein conductivity of said electroconductive layer is imparted by cuprous iodide.
  • electroconductive layer comprises binder and particles of cuprous iodide which are dispersed in said binder wherein conductivity of said electroconductive layer is imparted by cuprous iodide.
  • color forming layer comprises leuco form of triphenylmethane dyes or leuco form of fluoran dyes and an organic acid or a phenolic material which are separately dispersed in binders.
  • the color forming layer comprises a metal salt and an organic spot test reagent which rapidly reacts with metal ion of said metal salt to form a visible reaction product which are separately dispersed in binders 5 and either one of said two materials which has a lower melting point has a melting point of 70 150C.
  • the color forming layer comprises leuco form of an oxidation-reduction indicator dispersed in a 10 binder.
  • color forming layer comprises a metal chloride or oxide which forms color or changes color with reduction upon application of electric current and 15 which is dispersed in a binder.
  • An electro-recording sheet according to claim 1 which comprises a support of paper or plastic film,
  • a color forming layer comprising a metal salt and an organic spot test reagent dispersed in a binder which is provided on said electroconductive layer.

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  • Heat Sensitive Colour Forming Recording (AREA)
  • Fax Reproducing Arrangements (AREA)
  • Color Printing (AREA)
  • Laminated Bodies (AREA)
US320821A 1972-03-24 1973-01-03 Electrorecording sheet Expired - Lifetime US3871972A (en)

Applications Claiming Priority (1)

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JP47030088A JPS5133742B2 (enrdf_load_stackoverflow) 1972-03-24 1972-03-24

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US (1) US3871972A (enrdf_load_stackoverflow)
JP (1) JPS5133742B2 (enrdf_load_stackoverflow)
CA (1) CA968556A (enrdf_load_stackoverflow)
DE (1) DE2264108C3 (enrdf_load_stackoverflow)
FR (1) FR2177280A5 (enrdf_load_stackoverflow)
GB (1) GB1422391A (enrdf_load_stackoverflow)
NL (1) NL7217764A (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4046074A (en) * 1976-02-02 1977-09-06 International Business Machines Corporation Non-impact printing system
US4133933A (en) * 1975-06-27 1979-01-09 Matsushita Electric Industrial Co., Ltd. Electrosensitive recording sheet with support containing cuprous iodide particles
US4173677A (en) * 1976-06-21 1979-11-06 Sekisui Kagaku Kogyo Kabushiki Kaisha Electro-thermosensitive recording materials
US4263105A (en) * 1979-08-21 1981-04-21 Issec Sa Electrosensitive recording material and process
US4309255A (en) * 1980-09-10 1982-01-05 International Business Machines Corporation Electrochromic recording paper
US4444626A (en) * 1983-01-21 1984-04-24 International Business Machines Corporation Electrochromic printing
US5108861A (en) * 1990-08-28 1992-04-28 Xerox Corporation Evaporated cuprous iodide films as transparent conductive coatings for imaging members
US20160109371A1 (en) * 2013-05-09 2016-04-21 University Of Central Florida Research Foundation, Inc. A portable spectrometer for the presumptive identification of illicit drugs and substances of abuse
US11199498B2 (en) 2013-05-09 2021-12-14 University Of Central Florida Research Foundation, Inc. Portable spectrometer for the presumptive identification of substances
CN115784632A (zh) * 2020-12-07 2023-03-14 魏伟兴 一种高透型低辐射镀膜玻璃

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50134646A (enrdf_load_stackoverflow) * 1974-04-10 1975-10-24
JPS5137243A (ja) * 1974-09-25 1976-03-29 Jujo Paper Co Ltd Denkikannokirokutai
JPS5137657A (enrdf_load_stackoverflow) * 1974-09-26 1976-03-30 Canon Kk
JPS5233543A (en) * 1975-09-09 1977-03-14 Oji Paper Co Ltd Electroconductive thermal recording paper
FR2474739A1 (fr) * 1980-01-30 1981-07-31 Aussedat Rey Systeme et papier d'enregistrement electrosensible
JPS59120654A (ja) * 1982-12-27 1984-07-12 Shin Nisso Kako Co Ltd フルオラン化合物
JPS6016532U (ja) * 1983-07-08 1985-02-04 日新電機株式会社 モ−ルド形コンデンサ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411948A (en) * 1964-04-08 1968-11-19 Hewlett Packard Co Electrosensitive recording medium
US3434878A (en) * 1964-10-26 1969-03-25 Hewlett Packard Co Method of forming a multicolor electrosensitive recording medium and article
US3518038A (en) * 1965-10-20 1970-06-30 Allied Chem Electrographic recording mixture containing a morpholinyl diphenyl methane and 2 triphenyl methane
US3772159A (en) * 1970-12-25 1973-11-13 Jujo Paper Co Ltd Electrical recording medium and process for recording thereon

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1469975C3 (de) * 1960-09-19 1973-12-13 Eastman Kodak Co., Rochester, N.Y. (V.St.A.) Verfahren zum Aufbringen eines elektrisch leitenden und antistatischen Überzuges auf eine Oberflache
JPS4946953A (enrdf_load_stackoverflow) * 1972-09-09 1974-05-07

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411948A (en) * 1964-04-08 1968-11-19 Hewlett Packard Co Electrosensitive recording medium
US3434878A (en) * 1964-10-26 1969-03-25 Hewlett Packard Co Method of forming a multicolor electrosensitive recording medium and article
US3518038A (en) * 1965-10-20 1970-06-30 Allied Chem Electrographic recording mixture containing a morpholinyl diphenyl methane and 2 triphenyl methane
US3772159A (en) * 1970-12-25 1973-11-13 Jujo Paper Co Ltd Electrical recording medium and process for recording thereon

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133933A (en) * 1975-06-27 1979-01-09 Matsushita Electric Industrial Co., Ltd. Electrosensitive recording sheet with support containing cuprous iodide particles
US4046074A (en) * 1976-02-02 1977-09-06 International Business Machines Corporation Non-impact printing system
US4173677A (en) * 1976-06-21 1979-11-06 Sekisui Kagaku Kogyo Kabushiki Kaisha Electro-thermosensitive recording materials
US4263105A (en) * 1979-08-21 1981-04-21 Issec Sa Electrosensitive recording material and process
US4309255A (en) * 1980-09-10 1982-01-05 International Business Machines Corporation Electrochromic recording paper
US4444626A (en) * 1983-01-21 1984-04-24 International Business Machines Corporation Electrochromic printing
US5108861A (en) * 1990-08-28 1992-04-28 Xerox Corporation Evaporated cuprous iodide films as transparent conductive coatings for imaging members
US20160109371A1 (en) * 2013-05-09 2016-04-21 University Of Central Florida Research Foundation, Inc. A portable spectrometer for the presumptive identification of illicit drugs and substances of abuse
US10101278B2 (en) * 2013-05-09 2018-10-16 University Of Central Florida Research Foundation, Inc. Portable spectrometer for the presumptive identification of illicit drugs and substances of abuse
US11199498B2 (en) 2013-05-09 2021-12-14 University Of Central Florida Research Foundation, Inc. Portable spectrometer for the presumptive identification of substances
CN115784632A (zh) * 2020-12-07 2023-03-14 魏伟兴 一种高透型低辐射镀膜玻璃
CN115784632B (zh) * 2020-12-07 2024-04-09 河北金石信远新材料科技有限公司 一种高透型低辐射镀膜玻璃

Also Published As

Publication number Publication date
GB1422391A (en) 1976-01-28
JPS5133742B2 (enrdf_load_stackoverflow) 1976-09-21
DE2264108B2 (de) 1975-01-30
DE2264108A1 (de) 1973-10-04
JPS4896137A (enrdf_load_stackoverflow) 1973-12-08
CA968556A (en) 1975-06-03
FR2177280A5 (enrdf_load_stackoverflow) 1973-11-02
NL7217764A (enrdf_load_stackoverflow) 1973-09-26
DE2264108C3 (de) 1975-09-11
AU5073873A (en) 1974-07-04

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